Tb3NiSi2合金磁相变与磁热性能研究

依据X射线衍射(XRD)与等温磁化曲线和等磁场变温磁化曲线,主要研究了Tb₃NiSi₂合金相结构与磁性相变和磁热性能。XRD表明,采用800℃保温14天,然后炉冷至室温的热处理方法制备的R3NiSi2(R=Tb,Dy,Ho,Er)合金中,主相均为Gd3NiSi2型正交结构(空间群:Pnma,No.62)相,但杂相R5Si3含量存在差异,其规律是从Er到Tb,含量依次减少,Tb₃NiSi₂合金样品基本为一个单相,其相应晶格常数分别为a=1.1240(8)nm,b=0.41009(8)nm,c=1.12058(1)nm。等温磁化曲线显示在50~300 K温度范围内,Tb₃NiSi₂合金仅展现出铁磁-顺磁相变,并没有在130,82,66,53 K等观察到相关文献报道的多重的反常反铁磁态-铁磁态(AFM-FM)相变。0.01 T磁场下的磁化强度对温度求导曲线(d M/d T)和0~2 T磁场下的Arrott图结果证实合金铁磁-顺磁二级磁相变居里温度(Tc)=88 K。居里外斯定理拟合表明合金中Tb³⁺粒子的有效磁矩为9.90μB(μB为玻尔磁子),同期望值μeff/Tb³⁺=g(J(J+1))1/2=9.72μB基本一致。在磁热性方面,Tb₃NiSi₂合金在0~2 T磁场范围内,低场响应性较差,铁磁态分子的有效磁矩远低于顺磁分子有效磁矩,最大磁熵变(-ΔSM_max)为3.2 J·kg^-1·K^-1;在对应的半高宽温跨(δTFWHM)=35.5K范围内,相对制冷量为113 J·kg^-1。     

Magneto-Caloric Effect of Gd5Si2Ge2Compounds under Different Processing Conditions

The magneto-caloric effect of Gd5 Si2Ge2 compounds produced by various techniques is investigated in terms of their magnetization behaviors in the magnetic field from 0 to 2.0 T.The studied materials include arc-melted, annealed and sintered alloys.The results demonstrate that the Gd5Si2Ge2 alloys obtained under different processing conditions possess distinct magneto-caloric effect due to their various microstructures.Proper annealing treatment can enhance the magneto-caloric effect of the alloy remarkably.While the sintered alloy bears relatively lower value of magnetic entropy change ( △ SM) than arc-melted one.The magnetic entropy change of the annealed Gd5 Si2Ge2 alloy arrives the arrives the maximum value of - △SM = 15.29 J· kg-1· K-1 for magnetic field change under 2.0 T in the present work.     

Magnetocaloric effect in ErNi_2 melt-spun ribbons

ErNi2 ribbons were produced by rapid solidification using the melt spinning technique.Their structural,magnetic and magnetocaloric properties in the as-solidified state were studied by X-ray diffraction,scanning electron microscopy,magnetization and specific heat measurements.Samples are single phase with the MgCu_2-type crystal structure,a Curie temperature T_C of 6.8 K and a saturation magnetization at2 K and 5 T of 124.0 A·m~2/kg.For a magnetic field change μ_0△H of 5 T(2 T) ribbons show a maximum magnetic entropy change |△S_M~(peak)| of 24.1(16.9) J/(kg·K),and an adiabatic temperature change △T_(ad)~(max) of8.1(4.4) K;this is similar to the previously reported literature for bulk alloys that were processed through conventional melting techniques followed by prolonged thermal annealing.In addition,the samples also show slightly wider △S_M(T) curves with respect to bulk alloys leading to a larger refrigerant capacity.     

Thermodynamical Evaluation on Magnetocaloric Effect of Magnetic Refrigerating Materials Near Room Temperature

The relationship between isothermal magnetic entropy change △S and adiabatic temperature change △Tad was deduced according to the principles of thermodynamics. The MCE and the engineering application were discussed for Gd and several new kinds of magnetic refrigerating materials near room temperature, Gd5Si2Ge2, MnFeP0.45As0.55 and LaFe11.2Co0.7Si1.1. Isothermal entropy change is proportional to adiabatic temperature change with a factor of T/C (T is temperature, C is heat capacity). When the comparison of magnetacoloric effect is made for two different materials, we should consider isothermal entropy change as well as adiabatic temperature change.     

Magnetocaloric effect and magnetic properties of La_（0.9）Ce_（0.1）（Fe_（0.99）Mn_（0.01））_（11.6）Si_（1.4）H_（1.6） compound

Magnetocaloric effect and magnetic properties of La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4 and its hydride La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4H1.6 were investigated. The Curie temperature of La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4 was increased by hydrogen absorption. XRD patterns showed that the structure of La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4H1.6 remained NaZn13-type. The Curie temperature (TC) of the sample was increased from 174 K to 331 K. The homogeneity of the hydrogen absorption for La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4H1.6 was proven very well by the random measurement of DSC. The magnetic entropy △SM of La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4H1.6 had peak at 326 K. The peak value of-△SM-was 12.3 and 7.8 J/(kg.K) under magnetic field change of 0-2 T and 0-1 T,respectively,which was comparable with Gd5Si2Ge2. The negative slope and inflection point of the Arrott curve indicated that the first-order magnetic transition of La0.9Ce0.1(Fe0.99Mn0.01)11.6Si1.4 was reserved after hydrogen absorption.     

LaGd_(0.1)Fe_(11.4-x)Co_xSi_(1.6)(x=0.1,0.3,0.5,0.7,0.9)合金的磁热效应

研究了LaGd0.1Fe11.4-xCoxSi1.6(x=0.1,0.3,0.5,0.7,0.9)系列合金的结构以及磁热效应。室温XRD分析表明该系列合金除微量的α-Fe相外,均具有立方NaZn13型立方单相晶体结构,空间群为Fm-3c。晶格常数没有明显变化,分别为1.1458,1.1454,1.1458,1.1459,1.469nm。磁性测量表明该系列合金的Tc随着Co含量的增加而增加,分别为212,231,253,281,302K。在外磁场变化ΔB=1.5T时,最大的磁熵变随着Co含量的增加而减少,由x=0.1的13.8J降为x=0.9J.kg-.1K-1的1.5J.kg-.1K-1。并且随着Co含量的增加存在由一级相变转为二级相变的趋势。     

Glass Forming Ability and Magnetic Property of Fe74Al4Sn2 （PSiB）20 Amorphous Alloy

Amorphous ribbons of Fe74 Al4Sn2 (PSiB)20 alloy have been synthesized by melt spinning and axial design method. The thermal properties of the amorphous ribbons have been measured by differential scanning calorimeter (DSC). The DSC results show that the Fe74 Al4Sn2P12Si4B4 amorphous alloy has relatively wider supercooled liquid region with a temperature interval of 40.38 K (△TX=TX-TR). The alloys with a higher phosphorous content in the metalloid element composition triangle of Fe74Al4Sn2(PSiB)20 have high glass forming ability. The amorphous alloys also show good magnetic properties in which Fe74Al4Sn2P6.67Si6.67B6.67 alloy has a large maximum permeability (μm), Fe78AlSn2P3Si3B10 alloy exhibits a high squareratio (Br/Blo) and FeT~A14Sn2P, Sil2B4 shows a low core loss (P0.5 1.3T). High glass forming ability and good magnetic properties make Fe74Al4Sn2(PSiB)20 amorphous alloys valuable in future research.     

粉末冶金法制备La（Fe,Co,Si）13磁制冷合金

用非自耗电弧炉熔炼制备了LaFe10.8Co0.7Si1.5C0.2铸锭,并将该铸锭在石油醚的保护中球磨制粉,粉末经过压制后在氩气气氛中高温烧结2～8 h。用XRD和SEM检测了LaFe10.8Co0.7Si1.5C0.2铸锭及烧结后样品的相和组织结构。结果表明,LaFe10.8Co0.7Si1.5C0.2合金铸锭主要由α-Fe(Co,Si)相和1∶1∶1相组成,仅含有极少量1∶13相。采用粉末冶金法制备的合金相比传统工艺下合金的成相时间有明显缩短,仅烧结2 h就有一定比例的NaZn13型1∶13相生成,而且在1100℃烧结4 h时合金的成相最好,形成了以1∶13相为主相的合金,温度过高或过低所形成的1∶13相的相对含量都会减少。烧结时间增加或缩短也会导致1∶13相的相对含量减少。此外,还对在LaFe10.8Co0.7Si1.5C0.2粉末中加入LaFe0.9Co0.27Si1.17作为烧结助剂对合金成相的影响进行了研究。结果表明,加入烧结助剂后有助于合金的成相,加入质量分数为25%的LaFe0.9Co0.27Si1.17作为烧结助剂在1100℃烧结4 h所形成的合金几乎是单一的1∶13相,仅含极少量点状分布的富含镧的杂相。而LaFe10.8Co0.7Si1.5C0.2块状铸锭在1100℃退火4 h后仍含有α-Fe相和1∶1∶1相。可以看出,用粉末冶金法制备La(Fe,Co,Si)13磁制冷合金的热处理时间得到极大缩短。     

Effect of a magnetic field on magnetic entropy change in LaFe_（11.7）Si_（1.3） compound

The magnetocaloric effect of LaFe11.7Si1.3 compound was investigated under an external magnetic field up to 9 T.The magnetization changed drastically at the Curie temperature TC under different fields and TC increased with the applied fields.The magnetic entropy change |?SM| vs temperature peak consisted of a spike and a plateau.The spike was a spurious result,while the plateau part resulted from the field-induced itinerant-electron metamagnetic(IEM) transition above TC,which went up with magnetic fields increasing.The width of the magnetic entropy change increased with magnetic fields at a rate of dL?S /dT~4 K/T.     

Effect of Mn Substitution on Microstructure Evolution and Magnetic Phase Transition in La(Fe1−x Mn x )10.8Co0.7Si1.5 Compounds

The influences of Mn substitution for Fe on microstructures of La(Fe_1?x Mn _x )_10.8Co_0.7Si_1.5 (x = 0, 0.01, 0.02, 0.03) alloys in both the as-cast state and the annealed state have been studied. The results show that Mn substitution promotes the fining of the as-cast microstructure and increases the formation of 1:13 phase significantly when annealed. An almost single 1:13 phase is obtained for x = 0.01 when annealed at 1373 K (1100 °C) for 3 days, while a large amount of impurity phases is still present for x = 0. By increasing the amount of Mn to x = 0.02, a more purified annealed microstructure can be obtained. However, further substitution of Mn up to x = 0.03 is harmful for the formation of 1:13 phase. The Curie temperature T _C of the annealed La(Fe_1?x Mn _x )_10.8Co_0.7Si_1.5 (x = 0, 0.01, 0.02, 0.03) varies monotonously with Mn content x, decreasing from ~279 K (6 °C) for x = 0 to ~236 K (?37 °C) for x = 0.03. When x = 0.01, a higher maximum entropy change (?ΔS)_max of 5.3 J/(kgK) and relative cooling power (RCP) of 166 J/kg can be obtained under a magnetic field of 2T. Further substitution of Mn (x = 0.02) results in a slight decrease of (?ΔS)_max, whereas a larger RCP can still be kept.     

Phase structure and magnetocaloric effect of (Tb1-xDyx)Co2 alloys

Phase structure and magnetocaloric effect of (Tb1-xDyx)Co2 alloys with x=0, 0.2, 0.4, 0.6, 0.8, and 1.0 were investigated using X-ray diffraction analysis, differential thermal analysis, and magnetization measurement. The samples were single phase with cubic MgCu2- type structure; with the increase of Dy content, Tc decreased from 240 K (TbCo2) to 130 K (DyCo2), and the maximum magnetic entropy change |ΔSM,max| increased from 3.133 to 8.176 J/kg-K under low magnetic field of 0-2 T. The Arrott plot and the change of |ΔSM,max| showed that magnetic phase transition from second order to first order occurred with the increase of Dy content between x=0.6 and 0.8.     

Magnetic properties and magnetic entropy change of perovskite manganites La_(0.9-x)Eu_xSr_(0.1)MnO_3(x=0.000,0.075) by experimental method and numerical fitting

Polycrystalline samples La_(0.9-x)EuxSr_(0.1)MnO_3(x = 0.000, 0.075) were prepared by the standard solid-state reaction method. The results show that the samples preform a characteristic of clusters spin-glass state at low temperature. The samples show a characteristic of ferromagnetism(FM) characteristic in the temperature range of 15-125 K and 15-150 K respectively; the samples show preformed clusters in the temperature range of 125-343 K and 150-325 K, respectively, the samples show paramagnetism(PM)characteristic above 343 and 325 K, respectively. The second-order transitions are found at 118 and 135 K for undoped and doped sample, respectively. When the applied magnetic field is 7 T, the maximum magnetic entropy change |△S_M| value of the samples is near the Curie temperature(Tc), and the value of|△S_M| reaches 2.76 and 3.03 J/(K kg), respectively. In addition, the relative cooling power(RCP) is found to be 425.28 and 443.53 J/kg. The numerical fitting data fit well with experimental data. These results indicate that both the samples have the potential to realize magnetic refrigeration in the high temperature region(T 77 K).     

Effects of manganese doping on magnetocaloric effect in Ge-rich Gd_5Ge_（2.05）Si_（1.95） alloy

The structure, magnetic and magnetocaloric properties of the Ge-rich Gd5Ge2.05-xSi1.95-xMn2x (x=0.01 and 0.03) alloys were investigated by scanning electron microscopy, X-ray powder diffraction, differential scanning calorimeter (DSC) and magnetization measurements. The results of energy dispersive X-ray analysis (EDX) and X-ray diffraction analyses showed that the composition and crystal structure of the alloys were desired. DSC measurements were performed to determine the transformation temperatures for each alloy. Both alloys exhibited the first order phase transition around room temperature. The alloys showed an anti-ferromagnetic transition around 60 K. The isothermal magnetic entropy changes of the alloys were determined from the isothermal magnetization measurements by using the Maxwell relation. The maximum values of isothermal magnetic entropy change of the Gd5Ge2.05-xSi1.95-xMn2x alloy with x=0.01 was found to be -12.1 and -19.8 J/(kg·K) using Maxwell equation around 268 K in applied fields of 2 and 5 T, respectively.     

哈斯勒合金Ni-Mn-Sn的磁热效应

采用真空电弧熔炼法和高温淬火法制备了四元哈斯勒合金Ni50-xCuxMn36Sn14(x=0,2,4,6)的化合物。用X射线衍射仪和振动样品磁强计研究了合金的物相与磁热效应。结果表明,部分Cu元素对Ni的替代,并没有改变三元哈斯勒合金Ni-Mn-Sn原有的晶体结构,只是晶格常数开始有减小的趋势,晶胞的体积没有发生太大的变化。M-T曲线的结果表明,该系列哈斯勒合金样品在奥氏体相的铁磁交换作用增强,导致居里温度升高,而结构相变温度降低。此外,通过麦克斯韦方程计算了该系列合金的磁熵变(-ΔSm),在磁场变化为1.5 T的情况下,获得了Ni46Cu4Mn36Sn14合金在330 K附近的最大磁熵变(-ΔSmmax)约为2.0 J·(kg·K)-1。     

MnFe1-xTixP0.63Ge0.12Si0.25（x=0,0.01,0.02,0.03）系列化合物的磁热效应

通过X射线衍射分析(XRD)和振动磁强计(VSM)磁性测量,研究了替代元素Ti替代Fe元素含量的MnFe1-xTixP0.63Ge0.12Si0.25(x=0,0.01,0.02,0.03)系列化合物的物相结构与磁热效应的影响。结果表明:该系列化合物的结构为Fe2P型六角晶系结构,空间群为P62m。主相均为(Mn,Fe)2(P,Ge,Si),并含有少量的第二相(Mn,Fe)3Si相。随着Ti原子替代Fe原子的增加化合物的晶格常数a增大,晶格常数c略有减小,晶胞体积V基本保持不变。随着Ti含量增加居里温度(TC)减小,热滞ΔThys的大小改进不太明显。MnFeP0.63Ge0.12Si0.25的TC为305 K,当外磁场变化为0～1.5 T时最大磁熵变的绝对值为14.8 J.(kg.K)-1。     

Study of Magnetic Entropy Changes in Gd1-x Tx ( T = Ti, Cr, Fe and Cu) Alloys

Magnetic refrigeration techniques based on the magnetocaloric effect (MCE) were demonstrated as a promising alternative to conventional vapour-cycle refrigeration.Recently, scientists focused their research on room temperature magnetic refrigeration.The rare earth Gd metal is regarded as a prototype for room temperature magnetic refrigerant.Considering the various requirements in application, it is necessary to search for the magnetic refrigerant possessing qualities as good as Gd but having different Tc above or below room temperature.In this article, we report the magnetic entropy changes in Gd1 -xTx(T = Ti, Cr, Fe and Cu) alloys.With a small quantity of T atoms introduced in Gd, the Curie temperature increases.The values of magnetic entropy change in these alloys are almost the same as or a little less than that of Gd.But the refrigerant capacities of these alloys are obviously larger than that of Gd.All these facts suggest that Gd1-xTx(T = Ti, Cr, Fe and Cu) alloys may be good refrigerants for room temperature magnetic refrigeration.     

Ni_(43)Mn_(46-x)T_xSn_(11)(T=Fe,Co,Ni)合金的马氏体相变和磁熵变

通过示差扫描量热仪和振动样品磁强计对Ni43Mn46-xTxSn11(T=Fe,Co,Ni)铁磁形状记忆合金的相变、磁性以及磁熵变进行了研究。结果表明,由于价电子浓度的增加,Fe,Co,Ni替代Mn使马氏体转变温度大幅提高。Fe,Ni掺杂对马氏体居里温度(TCM)影响不大,Co则使TCM略有下降;奥氏体居里温度(TCA)对成分比较敏感,Fe,Ni的加入均使TCA略有提高,而Co则会大大提高TCA。由于马氏体相变伴随着磁化强度的突变,Ni43Mn46-xTxSn11合金在马氏体相变附近具有较大的低场磁熵变,对于Ni43Mn41Co5Sn11在室温1T磁场下磁熵变达到了19J.kg-.1K-1。通过调节成分,磁熵变峰值温度可以在199和294K之间调节,同时保持了较大低场磁熵变。     

Gd3-xMnxAl2系合金的晶体结构和磁熵研究

采用真空高频磁悬浮炉制备出一系列的Gd3-xMnxAl2(x=0,0.1,0.2,0.3)合金。通过Mn对Gd的部分替代,研究了Mn元素微量替代对Gd3Al2合金结构和磁熵的影响。实验结果表明,Gd3-xMnxAl2系合金的结构与Gd3Al2相同;随着Mn含量的增加,Gd3-xMnxAl2系合金的居里温度和磁熵发生了变化。说明Mn对Gd的部分替代改变了Gd3Al2合金的磁热效应。     

Phase transition and magnetocaloric effect of Ni55.2Mn18.6Ga26.2-xGdx (x=0, 0.05, 0.15) alloys

Phase transition process and magnetic entropy change -ΔS of Ni55.2Mn18.6Ga26.2-xGdx(x=0, 0.05, 0.15) alloys were studied.Ni55.2Mn18.6Ga26.2-xGdx(x=0, 0.05, 0.15) alloys still underwent simultaneous structural and magnetic transitions and transform from ferro-magnetic martensitic phase to paramagnetic austenitic phase during heating. Under a field of 2 T, the maximum magnetic entropy change -ΔSM of Ni55.2Mn18.6Ga26.15Gd0.05 alloy was 7.7 J/kg.K at 317 K during heating and 8.6 J/kg.K at 314 K during cooling while it was 11.8 J/kg.K at 317 K in Ni55.2Mn18.6Ga26.05Gd0.15alloy during heating.     

Magnetic Entropy Change of （Gd1-xREx）5Si4（RE = Dy, Ho） Alloys

Magnetic Entropy Change of (Gd_(1-x)RE_x)_5Si_4(RE=Dy, Ho) Alloys